Aliphatic polyepoxide-modified oxyalkylated phenol-aldehyde resins



Patented Feb. 19, 1963 ent polyepoxides are employed; in other words, if the ALIPHATIC ggggf QXYAL one described above is referred to as (B) and is essen- KYLATED PHENGLALDEHYDE RESINS tially hydrophile in character, then in comparison our Melvin De Groote, St. Louis, and Kwan-Tiug Shea, Brentaforementwned r y s 3121 93 93 5 19 N0. wood, M0. assigners m P n list; (i ti Wit. 5 393,224, is concerned with a combination obtained by a mington, Del, a corporation of Delaware stepwise process comparable to the one last mentioned No Drawing; Original application Nov. 19, 1953, set above in which final addition of (B) is replaced by the No. 393,223, now Patent No. 2,792,356, dated May 1 addition of a hydrophobe polyepoxide and thus is illus- 11957,6 hvided and this application Jan. 22, 1957, Ser. tratgd in the following manner:

The present application is a continuation-in-part of For an obvious reason, to wit, ease of comparison with our co-pending application, Serial No. 349,972, filed both of the two aforementioned applications, Serial No. April 20, 1953, now US. Patent No. 2,792,353, dated 349,972 and Serial No. 393,224, we are describing 2-step May 14, 1957, and a division of our copending applicaprocess of manufacture although obviously the two steps tion Serial No. 393,223, filed November 19, 1953, now could be fused or combined to be a single step, provided US. Patent No. 2,792,356 dated May 14, 1957. Said the same polyepoxide or the same type of polyepoxide,

first mentioned co-pending application is concerned with for instance, an essentially hydrophobe polyepoxide, is a process for breaking petroleum emulsions of the waterused. The single step procedure is illustrated subsein-oil type employing a demulsificr including the reaction 20 quently.

products of (A) certain oxyalkylated phenol aldehyde As has been pointed out in our aforementioned coresins, therein described in detail, and (B) certain nonpending application, Serial Number 337,884, filed Februaryl hydrophile polyepoxides, also therein described in my 19, 1953, there are two types of polyepoxides, pardetail, the ratio of rectant (A) to reactant (B) being in ticularly diepoxides, one being, for example characterized the proportion of 2 moles of (A) to one mole of (B). 5 by the formula:

The present invention relates to new chemical prodwherein R represents the divalent hydrocarbon radical of nets or compounds useful as demulsifying agents in proca dihydric phenol andn is an integer of the series 0, 1, esses or procedures particularly adapted for preventing, 2, 3, etc. More specifically, such diglycidyl ethers may breaking or resolving emulsions of the water-in-oil type be illustrated by the following formula:

and particularly petroleum emulsions. The new products ,wherein n is an integer of the series 0, 1, 2, 3, etc. are the reaction products of the above described reactants, In contradistinction to such diglycidyl ethers which (A) and (B), which are hereinafter described in detail, introduce an essentially hydrophobe radical or radicals, the ratio of reactant (A) to reactant (B), however, bethe present invention is characterized by analogous corniug in the proportion of 4 moles of (A) to 3 moles of pounds derived from diglycidyl ethers which do not intro- (B). duce any hydrophobe properties in its usual meaning but The present application thus diiters from the aforen fact are more apt to intfoducfi hydlophile Propertiei mentioned application in that one obtains products having s, th d P XidC employed in the present invention t le t t i th mglegular Weight b th use of a l l are characterized by the fact that the divalent radical conti f 4 moles f (A t 3 moles f (B), spficifically necting the terminal epoxide radicals contains less than 5 the product described in aforementioned co-pending apcarbon atoms in an interrupted chaininstance, a plication may beindicated th simple member and one of the most readily available members of the class of diepoxides described in our co- A' B A pending application, Serial No. 324,814, filed December In contradistinction the products herein described and 8, 1952, now abandoned, is useful for the resolution of petroleum emulsions may CH3 It is to be noted in this formula the terminal epoxy Products may be obtained by either a continuous procmdi a cal ar e a t l ess involving the two reactants or, if desired, by a 2-step S e S P fa ed by glvalent hydrophobe group method in which the final product described in aforc- H H mentioned co-pending application becomes an intermeo-0-tl -Go diate and is combined by means of another mole of (B), H E H in ratio of two moles of intermediate to one mole of The diepoxides employed in the present process thus are obtained from glycols such as ethylene glycol, 2 diethylene glycol, propylene glycol, dipropylene glycol,

tripropylene glycol, butylene glycol, dibutylene glycol, tri- In our co-pending application, Serial No. 393,224, butylene glycol, glycerol, diglycerol, triglycerol, and simifiled November 19, 1953, now US. Patent No. 2,792,357, lar compounds. Such products are well known and are reference is made to another product in which two diiiercharacterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be non-aryl or aliphatic in character. The diglycidyl ethers of our co-pending application, Serial No. 324,814, filed December 8, 1952, are invariably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compounds, such as glycenol or diglycerol with epichlorohydrin and subsequently with an alkali. Such diep'oxides have been described in the literature and particularly the patent literature. See, for example, Italian Patent 400,- 973, dated August 8, 1951; see, also, British Patent 518,057, dated December 10, 1938; and U.S. Patent No. 2,070,990, dated February 16, 1937, to Groll et al. Reference is made also to U.S. Patent No. 2,581,464, dated January 8, 1952, to Zech. This particular last mentioned patent describes a composition of the following general formula:

Lactation] R in which 2: is at least 1, z varies from less than 1 to more than 1, and x and 2 together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the hydroxyl groups thereof with the epoxide ether groups of the above formula, and any remaining groups of the residue being free hydroxyl groups.

It is obvious from what is said in the patent that variance can be obtained in which the halogen is replaced by a hydroxyl radical; thus the formula would become 0 Lasa na] X infusible. Furthermore, solubility is a factor insofar that t it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with a resin as described. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring i.e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxy-butane (1,2,3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydn'c phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U.S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed toward, products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Note, for example, that U.S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U.S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin. Simply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only six atoms thus:

Commercially available compounds seem to be largely to the former with comparatively small amounts, in fact comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any oxyalkylated phenolaldehyde resin by virtue of the fact that there are always present either phenolic hydroxyls or their alkanol radicals or the equivalent or alkanol radicals in the presence of any phenolic hydroxyl. Indeed, the products obtained by oxyalkylation of the phenolic resins must invariably and inevitably be oxyalkylation-susceptible.

To illustrate the products which represent the subject matter of the present invention, reference will be made to a reaction involving a mole of the oxyalkylating agent, i.e., the compound having two oxirane rings and an oxyalkylated resin. Proceeding with the example previously described, it is obvious the reaction ratio of two moles of the oxyalkylated resin to one mole of the oxyalkylat ing agent gives a product which may be indicated as follows:

in which n is a small whole number less than 10, and usually less than 4, and including 0, and R represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization oxyalkylated resin is simply an abbreviation for the oxyalkylated resin which is described in greater detail subsequently.

Such products must be soluble in suitable solvents such as a non-oxygenated hydrocarbon solvent or an oxygenated hydrocarbon solvent, or, for that matter, a mixture of the same with water. Needless to say, after the resin has been treated with a large amount of ethylene oxide, the products are water soluble and may be soluble in an acid solution.

The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distincty soluble in 5% acetic acid. For instance, the products freed from any solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances watersoluble, in fact, colloidally soluble.

Basic nitrogen atoms can be introduced into such derivatives by use of a reactant having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U.S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the waterin-oil type, and also for that matter for numerous other purposes where surface active materials are effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of mono-epoxides, in such manner that the derivatives so obtained have sufficient hydrophile character to meet at least the test set forth in U.S. Pacnt No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated derivatives obtained particularly by use of ethylene oxide, propylene oxide, etc., may not necessarily be xylenesoluble although they are xylene-soluble in a large numer of instances. If such compounds are not xylenesoluble the obvious chemical equivalent, or equivalent, chemical test, can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene the emulsification test includes such obvious variant.

Reference is made again to U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this text with the same force and effect as if it were herein included. This,

in essence, means that the preferred product for resolution of petroleum emulsions of the water-in-oil type is characterized by the fact that a 5050 solution in xylene, or its equivalent, when mixed with one to three volumes of Water and shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be divided into six parts, with Part 4, in turn, being divided into two subdivisions:

Part 1 is concerned with the hydrophile non-aryl polyepoxides, and particularly diepoxides, employed as reactants;

Part 2 is concerned with suitable phenol-aldehyde resins to be employed for reaction with the epoxides;

Part 3 is concerned with the oxyalkylation of the previously described phenol-aldehyde resins;

Part 4, Subdivision A, is concerned with the two-step procedure involving reaction between the two preceding types of materials and examples obtained by such reactions. It involves in essence preparation of an intermediate between 2 moles of the oxyalkylateid phenol-aldehyde resin and one mole of the diglycidyl ether, for example (identical With the products described in aforementioned co-pending application, Serial No. 349,972) followed by a second step in which 2 moles of these larger molecules are combined with use of a single mole of a diglycidyl ether or the like;

Part 4, Subdivision B, is a single step procedure resulting in substantially the same compounds by the use of 4 moles of the oxyalkylated phenol-aldehyde resin and 3 moles of the diglycidyl ether, or the equivalent;

Part 5 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 6 is concerned with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the non-aryl polyepo-xides and partic/ ularly diepoxides employed as reactants in the instant in vention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U.S. Patent No. 2,070,990, dated February 16, 1937 to Groll et al.; and U.S. Patent No. 2,581,464 dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U.S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula:

The diepoxides previously described may be indicated by the following formula:

in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH CH and n is 1. In another example previously referred to R" is CHzOCHz and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof, in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or,'as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R; is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol HOROH must be water soluble in substantially all proportions, i.e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linkedjl1ydrogen atoms were replaced by Thus, R(OH) where n represents a small whole number which is 2 or more, must be water-soluble. Such limita- '8 tion excludes polyepoxides it actually derived, or theoretically derived at least, from water-insoluble diols or water insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts. Referring to a compound 'of the type above in the formula in which R, is C H OH), it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C H (OH)OC H (0H), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

"or diepoxyalkanes. The diificulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The

principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in US. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially' para-tetra-decylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U.S. Patent No. 2,499,370, reference is made also to the following U.S. Patents: Nos. 2,499,365; 2,499,366; and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atom also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U.S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature, for instance, it has been stated that the composition is approximated in an idealized form by the formula R R n in the above formula 11 represents a small Whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers Where the total number of phenol nuclei varies from 3 to 6, i.e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical havingfrom 4 to 14 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde, it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

In the above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually, some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. The resin unit can be exemplified thus:

R R n R 10 in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation of resins, the kind herein employed as reactants, is well known. See U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few th of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i.e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trirner and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5; 4.5; or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purpose of convenience suitable resins are characterized in the following table:

TAB LE I M01. wt.

Exm of resin ample R Position derived n molecule number of R from (based on n+2) la Phenyl Para. Formal- 3. 992. 5

dehyde Tertiary butyL 3. 882. 5 Secondary butyl 3. 882. 5 Cyclohexyl 3. 1,025.5 Tertiary amyl..- do 3. 959. 5 Mixed secondary Ortho... do 3. 805. 5

and tertiary amyl.

Para .do

14a Tertiary amyl 3. 1, 022.5 15a Non 3. 1,330. 5 16a Tertiary butyl 3. 1, 071.5

17a Tertiary amyl 3. 5 1, 148. 5 18a Nonyluu. 3. 5 1, 456. 5 19a Tertiary butyl 3. 5 1, 008.5

20a Tertiary aznyl 3. 5 1, 085. 5 91a Nonyl 3. 5 1, 393. 5 22a Tertiary butyl 4. 2 996. 6

23a Tertiary amyl 4. 2 1, 083. 4 24a NOnyl 4. 2 1, 430. 0 25a Tertiary butyl 4.8 l, 094. 4 26a Tertiary amyl 4. 8 1,189.6 2711 Nonyl 4. 8 l, 570. 4 28a Tertiary amyl 1. 5 604. 0 29a Oyclohexyl 1. 5 646. 0 30 Hexyl 1. 5 653. 0 1. 5 688. 0

TABLE IV See U. S. Pat 557,0

Ethylene P pylene Flake Ex. No. Point Resin used Resin; oxide, oxide, Weight caustic Ex. No. on lbs. lbs. lbs. of xylene soda,

in graph ounces above on patent above patent A 1 Tert. amylphenol formaldehyde. 6 3 1 10 1 B .do 5 4 1 1 C 8 3 6 1 10 1 D 2 1 21. 5 2 5 25 2 E 9 1 9 2 F 6 1 10 15 25 2 G 3 1 2. 5 21. 5 25 2 H 7 5 1 1 1O 1 I 4 6 1 3 10 1 A 1 6 3 1 10 1 B 5 5 4 1 1O 1 C 8 8 6 1 10 1 D 2 1 21. 5 2 5 25 2 E 9 1 15 9 25 2 F 6 1 10 14 25 2 G 3 1 2.5 21.5 25 2 H 7 5 1 4 10 1 I 4 6 1 3 1O 1 A 1 6 3 1 10 1 B 5 5 4 1 10 1 G 8 3 6 1 10 1 D 1 21. 5 2 5 25 2 E 1 15 9 25 2 F 1 10 14 25 2 G 1 2. 5 21. 5 25 2 ll 5 1 4 10 1 I 6 1 3 10 1 Note the first series of nine compounds, 1d through 9d were prepared with propylene oxide, first and then ethylene oxide. The second nine compounds, 10d through 18d inclusive, were prepared using ethylene oxide first and then propylene oxide, and the last nine compounds, 19d through 27d, were prepared by random oxy-alkylation, i.e., using a mixture of the two oxides.

In the preparation of the resins, our preference is to use hydrocarbon substituted phenols, particularly parasubstituted, in which the substituted radical R contains 4 to 18 carbon atoms and particularly 4 to 14 carbon atoms. The amount of alkylene oxide introduced may be comparatively large in comparison to the initial resin. For instance, there may be as much as parts by weight of an oxide or mixed oxides used for each part by weight of resin employed.

It will be noted that the various resins referred to in the aforementioned US. Patent 2,499,370 are substantially the same type of materials as referred to in Table I. For instance, resin 3a of the table is substantially the same as 2a of the patent; resin 20:: of the table is substantially the same at 34a of the patent; and resin 38a of the table is the same as 3a of the patent.

In reaction with polyepoxides, and particularly diepoxides, a large number of the previously described oxyalkylated resins have been employed. 'For convenience, the following list is selected indicating the previously described compounds and their molecular weights. Such resins are generally employed as a 50% solution and the polyepoxide employed is a 50% solution, usually both reactants being dissolved in xylene and suflicient sodium methylate added to act as a catalyst, for instance, 1 to 2%.

TABLE V Molecular Example number weight TABLE V-Con tinned Example number PART 4 Subdivision A As previously pointed out, having the two types of reactants, i.e., the oxyalkylated phenol-aldehyde resins and the diglycidyl others or their equivalent, one can then proceed with either a single step reaction combining 4 moles of the oxyalkylated derivative with 3 moles of the diglycidyl ether or else one can employ a 2-step process in which one first combines 2 moles of the oxyalkylated phenol-aldehyde resin with one mole of the ether and then subsequently combines this product, which may be considered as an intermediate, with another mole of ether in the combination of 2 moles of the intermediate plus one mole of diglycidyl ether. For reasons previously indicated the instant part, i.e., Subdivision A, is concerned with a '2-step process. As previously pointed out, in the 2-step process the reactions which result in the formation of an intermediate involve two moles of an oxyalkylated phenol-aldehyde resin of the kind previously described and one mole of a diglycidyl ether as specified. The reaction is essentially an oxyalkylation reaction and thus may be considered as merely a continuance of the previous oxyalkylation reaction involving a monoepoxide as differentiated from a polyepoxide and particularly a diepoxide. The reactions take place in substantially the same way, i.e., by the opportunity to react at somewhere above the boiling point of water and below the point of decomposition, for example, -185 C. in the presence of a small amount of alkaline catalyst. Since the polyepoxide is non-volatile as compared, 'for example, with ethylene oxide, the reaction is comparatively simple. Purely from a mechanical standpoint it is a matter of convenience to conduct 'both classes of reactions in the same equipment. In other words, after the phenol-aldehyde resin has been reacted with ethylene oxide, propylene oxide or the like, it is subsequently reacted with a polyepoxide. The polyepoxide reaction can be conducted in an ordinary reaction vessel such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U.S. Patent No. 2,499,365. One can use a variety of catalysts in connection with the polyepoxide of the same class employed with monoepoxide. In fact, the reaction will go at an extremely slow rate without any catalyst at all. The usual catalyst includes alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chlorides. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. For practical purposes, it is best to use the same catalyst as is used in the initial oxyalkylation step and in many cases there is sufiicient residual catalyst to serve for the reaction involving the second oxyalkylation step, i.e., the polyepoxide. For this reason, we have preferred to use a small amount of finely divided caustic soda or sodium methylate as the initial catalyst and also the catalyst in the second stage. The amount generally employed is 1, 2 or 3% of these alkaline catalysts.

Actually the reactions of polyepoxides with various resin materials have been thoroughly described in the literature and the procedure is, for all purposes, the same as with glycide which has been described previously.

It goes without saying that the reaction involving the polyepoxide can be conducted in thefsame manner as the monoepoxide as far as the presence of an inert solvent is concerned, i.e., one that is not oxyalkylation-susceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The solvent so selected should be one which, of course, is suitable in the oxyalkylation step involving the monoepoxides described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required. Here again it has been our preference to have a solvent present in the oxyalkylation involving the initial stage and permitting the solvent to remain. The amount of solvent may be insignificant, depending whether or not exhaustive oxypropylation is employed. However, since the oxypropylated phenol-aldehyde resins are almost -siderably earlier stage.

invariably liquids there is no need for the presence of a V solvent as when oxyalkylation involves a solid which may not, .and also it is immaterial Whether there was solvent present in the second stage of oxyalkylation or not. The advantage of the presence of solvent is that sometimes it is a convenient way of controlling the reaction temperature and thus in the subsequent examples we have added sufficient xylene so as to produce a mixture which boils somewhere in the neighborhood of to C. and removes xylene so as to bring the boiling pointof the mixture to about 140 C. during part of the reaction and subsequently removing more xylene so that the mix ture refluxed at somewhere between 170 to 190 C. This was purely a convenience and need not be employed unless desired.

Example 1e The oxyalkylated resin employed was the one previous ly identified as 2b, having a molecular weight of 2169; the amount employed was 217 grams. The resin was dissolved in approximately an equal weight of xylene. The mixture was heated to just short of the boiling point of water, i.e., a little below 100 C. Approximately one half percent of sodium methylate was added, or, more exactly, 1.1 grams. The stirring was continued until there was a solution or distribution of the catalyst. The mixture was heated to a little past 100 C. and left at this temperature while 18.5 grams of the diepoxide (previously identified as A), dissolved in an equal weight of xylene, were added. After the diepoxide was added the temperature was permitted to rise to approximately 109 C. The time required to add the diepoxide was approximately one-half hour. The temperature rose in this period 'to about 127 C. The temperature rise was controlled by allowing the xylene to reflux over and to separate out the xylene by a phase separating trap. In any event, the temperature was raised shortly to 148150 C. and allowed to reflux at this temperature for almost three hours. Tests indicated that the reaction was complete at the end of this time; in fact, it probably was complete at a con- The xylene which had been separated out was returned to the mixture so that the reaction mass at the end of the procedure represented about 50% reaction product and 50% solvent. The procedure employed is, of course, simple in light of what has been said previously; in fact, it corresponds to the usual procedure employed in connection with an oxyalkylating agent such as glycide, i.e., a nonvolatile oxyalkylating agent. At the end of the reaction period the mass obtained was a dark, viscous mixture. It could be bleached, of course, by use of charcoal, filtering earths. or the like.

Various examples obtained in substantially the same manner as employed are described in the following tables:

TABLE VI Ex. Oxyalkyl- Amt, Diepox- Amt, Catalyst Xylene, Molar Time of Max. No. eted gins. ide used grus. (N 110C113), gins. ratio reaction, temp., Color and physical state resin grams hrs. C.

217 A 18. 5 1. 1 235. 5 2:1 3 '150 Dark. viscous mass. 460 A 18. 5 2.3 478.5 2:1 4 155 Do. 247 A 18.5 1.3 265. 5 2:1 3 152 D0. 609 A 18. 5 3.1 627. 5 2:1 5 i 158 Do. 249 A 18.5 1. 3 267. 5 2:1 3 a Do. 402 A 18.5 2.1 420. 5 2:1 4 150 Do. 708 A 18.5 3. 6 725. 5 2 :1 5 156 Do. 192 A 18.5 1.0 210.5 2:1 3 150 D0. 319 A 18.5 1. 6 337. 5 2:1 3 152 Do. 249 A 1. 9 1.2 251.0 2:1 3 155 D0. 217 B 11. 0 1.1 228.0 2:1 3 148 Do. 460 B 11.0 2.3 471.0 2:1 4 150 D0. 247 B 11.0 1.2 258.0 2:1 3 145 D0. 009 B 11. 0 3.1 620. 0 2:1 5 155 D0. 249 B 11. 0 1. 3 260 2:1 3 142 Do. 402 B 11.0 2.0 413 2:1 4 150 Do. 708 B 11.0 3.5 719 2:1 6 155 D0. 192 B 11.0 1.0 203 2:1 3 148 Do. 319 B 11. 0 1. 6 330 2:1 3 150 Do. 219 B 1. 1 1. 2 250 2:1 8 150 Do.

TABLE VII to a greater degree than one which does not contain free hydroxyl groups. Probable Note that in Table VIII temperatures varied as high as E N Oxyialkylmoleculfar Amomtof Amloun'tof 160 to 165 C. On the other hand in Table X wherea 53 ,gggg 3,5? 3,325 5 single-step process is used the temperature employed was Product between 80 and 90 C. The reason 1s merely that it is desirable to use the lowest temperatures which give comg. plete reaction based on the particular reactants employed. 5:310 5:310 21655 In many instances and in fact in most instances 80 to 12,550 1 275 31% 90 C. is sufiicient although higher temperatures can be 5,350 5,350 2,675 10 e 3,410 4,200 2,100 employed provided there 1s no gelation or cross-linking 14,530 7,265 3,632 and provided there is no objection to a somewhat darker 4,210 4,210 2,100 A 6,750 6,753 3,375 color. Everythlng else being equal additional solvent 505190 55020 2:510 tends 'to reduce cross-linking and, in any event, when the 4,560 4,550 2,230 9,420 4,710 2,355 reaction 13 complete it is preferable to eliminate alkalmlty 5,160 5,150 2,5 0 2 38 8 g8?) gg 1n the manner descnbecgzabovel. 1 s; 260 41130 21055 e 14, 380 7,100. 3,590 There s merely a continuation so as to change the re.-

288, 288 g gs: actant ratio in a previous derivative, to wit, nxam re 1c 50, 040 5,000 2,500 described above. Example 10, and other comparable 1 5 compounds are conveniently referred to as polyepoxidederived intermediate products. In any event, 235.5 In some instances there seems to be a change takes grams of this material dissolved in 244.8 grams of Xylene, place after the intermediate is allowed to stand for some along with a total of 2.4 grams of sodium inethylate -asla period of time with the residual catalyst present. The catalyst, were treated in exactly the same manner as prenature of this change is not well defined but it may be viously described, with 9.3- grams of diepoxide A. due to the fact that there is present a small amount of the is a molal ratio of 2:1 based on the intermediate to the polyepoxide unreacted, which reacts slowly. As a rule, diepoxide. The reaction time was two hours and'a mailiwhen the intermediate is to be stored for a period of mum temperature of 150 was employed. The retime and-then perhaps subjected to reaction with the same sultant product was a dark viscous mass. r polyepoxide or perhaps a ditferent polyepoxide of the Similar derivatives were obtained using other interme same general kind, we prefer to neutralize the added diates and also using diepoxide B previously described, caustic by the addition of a small amount of hydrochloric all of which is summarized in the two tables, following, acid, sulphuric acid, phosphoric acid, or an organic acid to wit, Tables VIII and .TAB t I I Polye gxide A Qatalyst- Tiine of Max. Ex. No. derive inter- Amt., Di'epox- Amt, (NaOOHs), Xylene, Molar reaction, tem Color and physical mediatetprodgms. ide used gms. grams grns. ratio hrs. state 235.5 A V9.3{ 2.4 244.8; 2:1 2 Dark 1556115111558. 478.5 A 9.3 4.8 487.3 21 2 D0. 265. 5 A 0-3 2. 7 274. s 2:1 2 Do. 627. 5 A 9.3 6. 3 .636. s 2: 1 2 150' Do. 267. 5 A 9 .3.-- 2.7 276,8 2:1 2 152 Do, 420. 0 A 10.3 4. 3 420. 3 2:1 2 158 Do. 725.5 A 0.3 7.3 735.8 21 2 154 Do. 210. 5 A 9. a 2. 2 210. 8 2:1 2 150 a Do. 337. 5 A 9. 3 3. 4 346. 8 2:1 2 153 Do. 501.0 A 1.9 5. 0 503. 8 2:1 2 162 Do. 223. 0 B 5. 5 2. 3 233. 5 2:1 2 160 Do. 471.0 B 5.5- 4.7 476.5 2:1 2 162 D0, 258.0 B 5.5 2.6. 263.5 2:1 2 105 Do. 620.0 B 5. 6 6. 2 025. 5 211 2 15s vno. 260.0 B 5.5 2.6 2 5.5 2:1 2 160 Do. 413.0 B 5.5 4.2 418.5 2:1 2 160 D0. 719. 0 B 5. 5 7. 2 724, 5 2:1 .2. 165 D0. 203.0 B 5. 5- 2.1 208.5 2:1 2. 156-. Do. 330.0 B 5.5 3.4 1 335.5 2:1 2 162 D0. 500. 4 B 1.1 5. 0 501. 5 2:1 2, 165 130.

such as toluene sulfonic acid. A p olydecylatedbenzene V 7 I i I 7 51,555 I); sulphonic is suitable. b

P'roba 10 If the mtfarmedlate is converiedass 3 2 Oxynlkylated molecular Amount of Amount of the 2:1 ratio to the 4:3 ratio then 111 that event there 13 Ex. No. resin. wl;. product; solvent, no need to neutralize the catalyst present. Indeed, such 60 used grams grams. catalyst is taken, into consideration in calculating the amount of catalyst present. In other words, one need 4, 395 2,448 not add as much catalyst when the residual catalyst 1s 3. 902;; 1,951 present as one would have to add if it had been previously $3 2. 5: gig neutralized. g. 22%.- Reference to the 4:3 ratio means there can be some 5830" 2}343 variation within reasonable limits, for instance, several 3 232" percent one way or the other. In other words, one could 41030- 21015 use, for example, 3.9 or 4.1 moles instead 01$ 4 moles, or 3:213 @333 one might use 2.9 or 3.1 moles insteadof moles. As the $82 28% 11101111 ratio of the polyepoxide to oxyalkylated resin in- 21124 1: 062 creases, i.e., approaches a 1:1 ratio there is greater opporgig 'gg tuni'ty for cross-linking or side reactions; or, stated an- 41170 21 085 other way, gelation is more apt to take place. This is i: .2333 true of a polyepoxide which includes free hydroxyl groups 1 such as ethylene imine or propylene imine, to produce wherein R, and R" are alkyl groups.

amazes 19 Subdivision B Example lee This is a one-step procedure which in essence produces the same end products as in the case of Example la in Table VIII, preceding. 217 grams of the oxyalkylated resin previously identified as Example 2b, were reacted with 27.8 grams of diepoxide A. The amount of catalyst used was 1.3 grams of sodium methylate. The amount of xylene used was 235.5 grams. The molal ratio of oxyalkylated resin to diepoxide was 4:3. The reaction time was approximately 3.5 hours. The maximum temperature employed was 84 C. The end product, of course, was substantially the same as that obtained under the heading of Example 1e, preceding. For this reason no additional data are included in regard to probable molecular weight, etc., as appeared in Table IX, for the reason that it is in essence identical as far as Example 12 is concerned and similarly, the data in regard to Example 2ee in Table X are substantially identical in regard to Ex- It is not necessary to point out that after reaction with a reactant of the kind described which introduces a basic nitrogen atom that the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part Five, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part Four preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and Waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and nordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into ample 22 in Table IX. an oil or gas well for purpose of removing a mud sheath,

TABLE X Oxy- Time 01 Max. Ex. alkyl- Amt, Dlepox- Amt, gggg fi Xylene, Molar reaction, temp., Color and physical state No. ated gms. ide used gms. m5 3 gms. ratio hrs. 0.

resin 217 A 27. 8 1. 3 235. 5 4:3 3. 5 84 Dark viscous mass. 460 A 27. 8 2. 5 478. 5 4:3 4. 5 85 Do. 247 A 27. 8 1.5 265. 5 4:3 4.0 85 Do. 609 A 27. 8 3. 2 627. 5 4:3 5.0 88 Do. 249 A 27. 8 1. 4 267. 5 4:3 3. 5 87 Do. 402 A 27. 8 2. 4 420. 5 4:3 4.0 83 Do. 708 A 27. 8 3. 6 726. 5 4:3 4. 5 82 Do. 192 A 27.8 1. 2 210. 5 4:3 4. 0 81 Do. 319 A 27. 8 1. 8 337. 5 4:3 5. 0 85 Do. 249 A 2.8 1. 4 251. 0 4:3 4. 5 84 Do.

PART 5 ence should be to Examples 1e or lee, herein described.

PART 6 The products, compounds, or the like herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-inoil type as described in detail in Part Five immediately preceding.

Such products can be reacted with alkylene imines,

cationactive materials. Instead of an imine, one may employ what is somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure.

7o H |3 R HnCN increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosive inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-in-water emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is 1. The products obtained by reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and

(B) a non-aryl hydrophile polyepoxide containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxy- 21 gen-linked hydrogen atom in a water-soluble poly- ;hydric alcohol by the radical said polyepoxides being free from reactivefuncti'onal groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said oxyalkylated phenolaldehyde resins, reactant (A) being the products derived by oxyalkylation involving (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide, and

(bb) a fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O) in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of four moles of (A) to three moles of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. The products obtained by reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a non-aryl hydrophile diepoxide containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical said diepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; said oxyalkylated phenol-aldehyde, resins reactant (A) being the prodducts derived by oxyalkylation involving (an) an alpha-betaalkylene' oxide'having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide, and (M) a fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed'in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O) in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of four moles of (A) to three moles of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of $01- vent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

3. The products obtained by reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a hydroxylated diepoxy polyglycerol containing two terminal 1,2-epoxy rings and having not over 20 carbon atoms; said oxyalkylated phenol-aldehyde resin, reactant (A) being the product derived by oxyalkylation involving (aa) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide, and (bb) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is selected from the group consisting of phenyl and saturated hydrocarbon radicals having not more than 24 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O) in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 120; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent 10 at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of four moles of (A) to three moles of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solventsoluble liquids and solids melting below the point of References Cited in the file of this patent UNITED STATES PATENTS 15 2,521,912 Greenlee Sept. 12,1950 2,626,942 De Groote Jan. 27, 1953 2,854,428 De Groote et al Sept. 30, 1958 

1. THE PRODUCTS OBTAINED BY REACTING (A) AN OXYLKYLATED PHENOL-ALDEHYDE RESIN CONTAINING A PLURALITY OF ACTIVE HYDROGEN ATOMS, AND (B) A NON-ARYL HYDROPHILE POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS AND HAVING TWO TERMINAL 1,2-EPOXY RINGS OBTAINED BY REPLACEMENT OF AN OXYGEN-LINKED HYDROGEN ATOM IN A WATER-SOLUBLE POLYHYDRIC ALCOHOL BY THE RADICAL 